CN107459535A - The iridium of poly-substituted quinoline coordination is miscellaneous with compound and preparation method and application - Google Patents
The iridium of poly-substituted quinoline coordination is miscellaneous with compound and preparation method and application Download PDFInfo
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- CN107459535A CN107459535A CN201710858082.7A CN201710858082A CN107459535A CN 107459535 A CN107459535 A CN 107459535A CN 201710858082 A CN201710858082 A CN 201710858082A CN 107459535 A CN107459535 A CN 107459535A
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- China
- Prior art keywords
- iridium
- quinoline
- methyl
- reaction
- ethyl acetate
- Prior art date
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 118
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 117
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 160
- 239000000463 material Substances 0.000 claims abstract description 68
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 61
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 61
- 238000006467 substitution reaction Methods 0.000 claims abstract description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 4
- 238000007086 side reaction Methods 0.000 claims abstract description 4
- 238000007171 acid catalysis Methods 0.000 claims abstract description 3
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 210
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 125
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 75
- 229910052757 nitrogen Inorganic materials 0.000 claims description 66
- 239000003208 petroleum Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 238000006073 displacement reaction Methods 0.000 claims description 52
- 150000003248 quinolines Chemical class 0.000 claims description 45
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 44
- 125000003118 aryl group Chemical group 0.000 claims description 42
- 238000001914 filtration Methods 0.000 claims description 40
- 239000000539 dimer Substances 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 39
- 150000002170 ethers Chemical class 0.000 claims description 38
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- -1 normal-butyl Chemical group 0.000 claims description 30
- 238000007605 air drying Methods 0.000 claims description 29
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 19
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 15
- 150000001805 chlorine compounds Chemical class 0.000 claims description 15
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 235000011009 potassium phosphates Nutrition 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 7
- 230000005587 bubbling Effects 0.000 claims description 7
- NQVLOHKMEASTMW-UHFFFAOYSA-N 4-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1C1=CC=C(N)C=C1 NQVLOHKMEASTMW-UHFFFAOYSA-N 0.000 claims description 6
- 229910019213 POCl3 Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 claims description 6
- GKOZUEZYRPOHIO-FTXFMUIASA-N iridium-187 Chemical compound [187Ir] GKOZUEZYRPOHIO-FTXFMUIASA-N 0.000 claims description 6
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- XAQPRWZOWQESKZ-UHFFFAOYSA-N 2-chloro-4-methyl-6-(4-methylphenyl)-3-phenylquinoline Chemical class ClC1=NC2=CC=C(C=C2C(=C1C1=CC=CC=C1)C)C1=CC=C(C=C1)C XAQPRWZOWQESKZ-UHFFFAOYSA-N 0.000 claims description 5
- GCPPBLOCBQIMAO-UHFFFAOYSA-N 2-chloro-6-methyl-4-(4-methylphenyl)quinoline Chemical compound ClC1=NC2=CC=C(C=C2C(=C1)C1=CC=C(C=C1)C)C GCPPBLOCBQIMAO-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 230000005622 photoelectricity Effects 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- WOVRXMQYJDFRON-UHFFFAOYSA-N 2-(4-methylphenyl)quinoline Chemical compound C1=CC(C)=CC=C1C1=CC=C(C=CC=C2)C2=N1 WOVRXMQYJDFRON-UHFFFAOYSA-N 0.000 claims description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 3
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- NGSFWDVZDPNLDW-UHFFFAOYSA-N 6-methyl-4-(4-methylphenyl)quinoline Chemical compound CC=1C=C2C(=CC=NC2=CC=1)C1=CC=C(C=C1)C NGSFWDVZDPNLDW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- NJIAKNWTIVDSDA-FQEVSTJZSA-N 7-[4-(1-methylsulfonylpiperidin-4-yl)phenyl]-n-[[(2s)-morpholin-2-yl]methyl]pyrido[3,4-b]pyrazin-5-amine Chemical group C1CN(S(=O)(=O)C)CCC1C1=CC=C(C=2N=C(NC[C@H]3OCCNC3)C3=NC=CN=C3C=2)C=C1 NJIAKNWTIVDSDA-FQEVSTJZSA-N 0.000 claims description 2
- IDMPWYKAKXWPFM-UHFFFAOYSA-N ethyl 2,5-dimethyl-3-oxohexanoate Chemical class CCOC(=O)C(C)C(=O)CC(C)C IDMPWYKAKXWPFM-UHFFFAOYSA-N 0.000 claims description 2
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 10
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims 4
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- QUBBAXISAHIDNM-UHFFFAOYSA-N ethyldimethylbenzene Natural products CCC1=CC=CC(C)=C1C QUBBAXISAHIDNM-UHFFFAOYSA-N 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- ILWSDHKEXWHUCY-UHFFFAOYSA-N 6-methyl-2,4-bis(4-methylphenyl)quinoline Chemical compound C1=CC(C)=CC=C1C1=CC(C=2C=CC(C)=CC=2)=C(C=C(C)C=C2)C2=N1 ILWSDHKEXWHUCY-UHFFFAOYSA-N 0.000 claims 1
- VEFYQEHKYMAEBW-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.C1C(CCCC1)P Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.C1C(CCCC1)P VEFYQEHKYMAEBW-UHFFFAOYSA-N 0.000 claims 1
- YXPUNWKYPJPPFC-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P YXPUNWKYPJPPFC-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 claims 1
- 229940125904 compound 1 Drugs 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000006471 dimerization reaction Methods 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 39
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 238000005160 1H NMR spectroscopy Methods 0.000 description 29
- 239000011368 organic material Substances 0.000 description 17
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 17
- 239000004926 polymethyl methacrylate Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 10
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002346 layers by function Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 5
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- FZFRYQHIQUEAAV-UHFFFAOYSA-N 2,8-dimethylnonane Chemical compound CC(C)CCCCCC(C)C FZFRYQHIQUEAAV-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000005594 diketone group Chemical group 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000005059 solid analysis Methods 0.000 description 3
- KBPCCVWUMVGXGF-UHFFFAOYSA-N 2,6-dimethylheptane Chemical compound CC(C)CCCC(C)C KBPCCVWUMVGXGF-UHFFFAOYSA-N 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KUKCUROTFRBUNU-UHFFFAOYSA-N Daucic acid Chemical compound OC1C=C(C(O)=O)OC(C(O)=O)C1O KUKCUROTFRBUNU-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid group Chemical group C(CC(=O)O)(=O)O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ASEZRLHCGAZIKP-UHFFFAOYSA-N (1,5-dimethylcyclohexa-2,4-dien-1-yl)boronic acid Chemical compound CC1=CC=CC(C)(B(O)O)C1 ASEZRLHCGAZIKP-UHFFFAOYSA-N 0.000 description 1
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical class FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 1
- XIBFIOFSBLXRDI-UHFFFAOYSA-N 1-(2,6-dichlorophenyl)-2-methylguanidine Chemical compound CNC(=N)NC1=C(Cl)C=CC=C1Cl XIBFIOFSBLXRDI-UHFFFAOYSA-N 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- BFOLTWPPFRDDNF-UHFFFAOYSA-N Cc(cc1)ccc1-c1c(cc(C)cc2)c2nc(O)c1 Chemical compound Cc(cc1)ccc1-c1c(cc(C)cc2)c2nc(O)c1 BFOLTWPPFRDDNF-UHFFFAOYSA-N 0.000 description 1
- PESOTAWRBXZLFY-UHFFFAOYSA-N OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.N Chemical compound OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.OP(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.N PESOTAWRBXZLFY-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- YJLPIKFDEXHCNQ-UHFFFAOYSA-N iridium;quinoline Chemical class [Ir].N1=CC=CC2=CC=CC=C21 YJLPIKFDEXHCNQ-UHFFFAOYSA-N 0.000 description 1
- 229940059939 kayexalate Drugs 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 229950011087 perflunafene Drugs 0.000 description 1
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
It is miscellaneous with compound and preparation method thereof, and application of the compound in terms of electroluminescent material the invention discloses a kind of iridium of poly-substituted quinoline coordination.3,5 is disubstituted in the ligand modified phenyl including 2 substitutions of the compound（Rd Rd）, 4 substitutions（Re）With 3,4,5 three substitutions（Rd Re Rd）Phenyl, the iridium of poly-substituted quinoline coordination is miscellaneous to be with the specific synthesis path of compound：Polysubstituted quinoline is generated by the Skraup ring-closing condensation reactions under amine ester exchange reaction, acid catalysis and hydroxyhalide reaction, then part can be obtained by Suzuki coupling reactions.This path avoids the reaction of the suzuki couplings of alkyl and the side reaction of multiple reaction sites competition, can improve combined coefficient and reduce purification difficulty.According to the spectral signature of these molecules and compound transformation function, very clearly this eka-iridium is miscellaneous can apply with compound as electroluminescent material in organic photoelectric electrical equipment.
Description
Technical field
The invention belongs to technical field of electronic materials, and in particular to the iridium of poly-substituted quinoline coordination is miscellaneous to match somebody with somebody compound and its system
Preparation Method, and application of the compound in terms of electroluminescent material.
Background technology
Just become to be becoming increasingly popular using the phototube device of luminous organic material, and have very the reason for they are welcome
It is more：Luminous organic material is relatively cheap, therefore organic electro-optic device has potential cost advantage relative to inorganic device.This
Outside, the inherent characteristic of organic material, such as its pliability, them can be made to be very suitable for some special applications, in flexible substrate
Processing.Organic photoelectric device device includes Organic Light Emitting Diode (OLED), organic transistor, organic solar batteries and organic
Photodetector.For OLED, luminous organic material has the advantage in performance compared to traditional material.For example, organic light emission
The luminous wavelength of layer can generally be easy to be adjusted with appropriate dopant.
The energy conversion pattern of luminous organic material is directly to convert electrical energy into luminous energy, relative to phosphor,
Luminous organic material can be closer to the demand in terms of photopic adaptation.Based on the manufacture of Organic Light Emitting Diode (OLED) technology
Display and the flexible profile of light-emitting instrument, and many artistic elements are added in electronic device.Earliest organic electroluminescence
Luminescent device developed by Eastman Kodak, be used as hole transmission layer, 8-hydroxyquinoline by aromatic amine organic molecule
Aluminium is as luminescent layer (" Organic electroluminescent diodes " Tang, Vanslyke etc., Appl Phys
Lett, volume 51, the 913-915 pages, 1987).This kind of device using organic molecule as core luminescent material is referred to as to have
Machine light emitting diode (OLED), can apply to new display and lighting field, have many advantages, such as and potentiality.Organic material
The luminescent device of preparation has the advantages that high-quantum efficiency, high brightness, high-luminous-efficiency；The hair being prepared into by luminous organic material
There is the advantage such as light, thin, soft, it is that other luminescent materials can not be by comparison that can especially be prepared into flexible apparatus in light device profile
The advantages of.Classified according to the electroluminescent material of core, traditional OLED can be divided into fluorescence class OLED and phosphorescence class
OLED.Compared with fluorescence OLED (theoretical luminous efficiency highest 25%), phosphorescent OLED (theoretical luminous efficiency 100%) due to
Higher luminous efficiency and as the main flow direction of OLED technology research and development.
Decay of the exciton from singlet excited to ground state, which produces, quickly to light, i.e. fluorescence.Exciton is from triplet excited state to base
The decay of state produces light, i.e. phosphorescence.Because the strong Quantum geometrical phase (ISC) of heavy metal atom can effectively strengthen substance
Electron spin state between excitation state and triplet excited state intersects change, phosphorescent metal complex, such as platinum complex, has shown
They harvest both substance and triplet excited state and reach the potentiality of 100% internal quantum.Therefore, phosphorescent metal is complexed
Thing is the fine candidate material as organic luminescent device (OLED) light emitting layer dopant, it academic and industrial circle all with
To very more attentions.And in the past ten years, people take on the commercialized road of technological direction high profit
Certain achievement was obtained, for example, OLED is applied in the advanced display of smart mobile phone, television set and digital camera.
Iridium (III) complex compound is a kind of widely used phosphor material, such as green glow complex：Fac- triphenylpyridinium bases
Iridium, i.e. fac-tri (2-phenylpyridinato) iridiums (III) [Ir (ppy)3]；Red emitting material：Double (2-
(2'- benzothienyls) pyridine-N, C3') (acetylacetone,2,4-pentanedione) conjunction iridium, i.e. bis [2- (2 '-benzothienyl) pyridinato-
N,C3’](acetylacetonato)iridium(III) [Btp2Ir(acac)]；Blue light emitting material：Double (4,6- difluorobenzenes
Yl pyridines-N, C2) pyridinecarboxylic conjunction iridium, i.e. bis [(4,6-difluorophenyl) pyridinato-N, C2]
(picolinato) iridium (III) (FIrpic) (" 100%phosphorescence quantum efficiency of
Ir(III)complexes in organic semiconductor films Yuichiro Kawamura, Kenichi
Goushi ", Jason Brooks etc., Appl Phys Lett, volume 86,2005).Although above-mentioned luminous organic material is manufacturing
It has been commercialized in terms of oled panel and ligthing paraphernalia, but these materials still have many rooms for promotion, for example reduce material
Preparation technology cost, the basic photoelectric properties for improving material, lifting final products application experience quality, reduce material in device processing procedure
Expect supporting cost, and improve material overall tolerability and weatherability etc. after device is integrated.
In the prior art, (US20120181511) discloses the synthesis of 5 mono-substituted quinoline parts and its Ir complexs
And its application in organic electro-optic device；(US2016093808) 4 or 5 mono-substituted quinoline parts and its Ir are disclosed
The synthesis of complex and its application in organic electro-optic device；(WO2016072780) 4,6 substd quinolines parts are disclosed
And its synthesis of Ir complexs and its application in organic electro-optic device, red light material used in the part synthetic method
The synthesis path of molecular structure for initiation material, is obtained double halogens by Skraup synthetic methods and substituted with malonic acid (daucic acid)
Key intermediate.This intermediate is coupled to obtain part by two step suzuki, and final red light material is obtained finally by coordination.
This paths has very more competitive side reactions, it is necessary to carefully be separated by column chromatography per single step reaction, and efficiency is very low,
The part actual recovery up to 10% or so of document report.And also related in reacting and introduce the anti-of alkyl suzuki couplings
Should, condition is harsh, and cost is high.In summary factor, by the material manpower that known industrial path is prepared and material into
This is very high, and purification difficulty is extremely big, and produces substantial amounts of waste residue and waste liquid.
It is miscellaneous with compound and preparation method thereof, and the compound the invention discloses a kind of iridium of poly-substituted quinoline coordination
Application and related photoelectricity physical property in terms of electroluminescent material.The preparation path and method being directed to are preparing take more
It is miscellaneous excellent with having in compound versatility, high efficiency and volume production cost to be adapted to etc. for the iridium of quinoline (position of quinoline 3,4,6) coordination
Point.2 poly-substituted quinoline parts for polysubstituted phenyl are complexed to be formed miscellaneous with Ir and match somebody with somebody compound, can increase substantially hair
The fluorescence quantum efficiency (PLQE) of luminescent material molecule.Function is transformed according to the spectral signature and compound of these molecules, very clearly
This quasi-molecule can be used for preparing the OLED related devices and application implements of high quality.
The content of the invention
The technical problems to be solved by the invention are：Disclose a kind of coordination of poly-substituted quinoline iridium it is miscellaneous with compound and its
Preparation method, and application of the compound in terms of electroluminescent material.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is:A kind of poly-substituted quinoline coordination is provided
Iridium it is miscellaneous match somebody with somebody compound, there is following molecular structural formula：
Ra,Rb,Rc ReRepresent hydrogen atom, D-atom, (C1-C6) alkyl substituent or aryl substituent (related substituents
Can by it is deuterated, substitute containing (C1-C6) alkyl or aryl substitutes).RdRepresent hydrogen atom or (C1-C6) alkyl substituent.
Rf,RhRepresent (C1-C6) alkyl substituent and aryl substituent (related substituents can by it is deuterated, take containing (C1-C6) alkyl
Generation or aryl substitution).
The alkyl containing 1-6 carbon atom of (C1-C6) alkyl groups mean linear or side chain, this kind of alkyl include first
Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, 1- methyl butyls, 2- methyl butyls, 3- first
Base butyl, 1,2- dimethyl propyls, 2,3- dimethyl propyls and 1- ethyl propyls, cyclopenta, cyclohexyl, 2- methyl -3- amyl groups,
3,3- dimethyl -2- butyl.
The miscellaneous molecular structural formula with compound of iridium of the poly-substituted quinoline coordination can be divided into following six kinds of structures, order respectively
Entitled molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula VI or molecular formula VII:
Molecular formula II:Ra-c、RfFor D-atom or (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-C6)
Alkyl substituent；
Molecular formula III:Rb-c、RfRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-
C6) alkyl substituent；
Molecular formula IV:Ra-b、RfRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-
C6) alkyl substituent；
Molecular formula V:Rb-c,Re,RfRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent；
Molecular formula VI:Ra-b、Re,RfRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent, RdRepresent
(C1-C6) alkyl substituent；
Molecular formula VII:Ra-c、Re-fRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent.
The miscellaneous iridium of poly-substituted quinoline coordination with compound is from by hereinafter complex of iridium 1 to 225 groups of complex of iridium
Into group in select.
The miscellaneous method with compound of iridium of above-mentioned poly-substituted quinoline coordination, its synthesis path are as follows:
In addition, present invention also offers miscellaneous the answering in terms of electroluminescent material with compound of the iridium of poly-substituted quinoline coordination
Use
The beneficial effects of the invention are as follows:Compared with prior art, the invention discloses a kind of novel electroluminescent material
The iridium of material ----poly-substituted quinoline coordination is miscellaneous with compound and preparation method thereof, the compound correlation photoelectricity physical property, and
Application of the compound as electroluminescent material in photoelectricity electrical equipment.The preparation path and method being directed to are preparing take more
It is miscellaneous excellent with having in compound versatility, high efficiency and volume production cost to be adapted to etc. for the iridium of quinoline (position of quinoline 3,4,6) coordination
Point.2 poly-substituted quinoline parts for polysubstituted phenyl are complexed to be formed miscellaneous with Ir and match somebody with somebody compound, can increase substantially luminous
The fluorescence quantum efficiency (PLQE) of material molecule.According to these molecules spectral signature and compound transform function, very clearly this
Quasi-molecule can be used for preparing the OLED related devices and application implements of high quality.
Brief description of the drawings
Fig. 1 is the miscellaneous OLED with compound as EL material of iridium being coordinated using poly-substituted quinoline of the present invention
Structure chart
Fig. 2 is launching light spectrogram of the complex of iridium 7 in CH2Cl2, PMMA at room temperature
Fig. 3 is the luminous I-V diagram of OLED made of complex of iridium 7 under normal temperature
Fig. 4 is the glow current efficiency chart of OLED made of complex of iridium 7 under normal temperature
The electroluminescent spectrum of OLED made of Fig. 5 complex of iridium 7
Embodiment
The iridium of poly-substituted quinoline coordination of the present invention is miscellaneous to match somebody with somebody compound, and its molecular formula is divided into I-VII type, I type as follows
Molecular formula is：
Ra,Rb,RcReHydrogen atom is represented, D-atom, (related substituents can for (C1-C6) alkyl substituent or aryl substituent
With by it is deuterated, substitute containing (C1-C6) alkyl or aryl substitutes).RdRepresent hydrogen atom or (C1-C6) alkyl substituent. Rf,
RhRepresent (C1-C6) alkyl substituent and aryl substituent (related substituents can by it is deuterated, substitute containing (C1-C6) alkyl
Or aryl substitution).
The alkyl containing 1-6 carbon atom of (C1-C6) alkyl groups mean linear or side chain, this kind of alkyl include first
Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, 1- methyl butyls, 2- methyl butyls, 3- first
Base butyl, 1,2- dimethyl propyls, 2,3- dimethyl propyls and 1- ethyl propyls, cyclopenta, cyclohexyl, 2- methyl -3- amyl groups,
3,3- dimethyl -2- butyl.
In I type molecule, RfAnd Rh, it is separate, represents (C1-C6) alkyl chain generally, RfAnd RhPhase
It is mutually consistent；
In I type molecule, Ra,RbAnd RcIt is separate, represents a hydrogen atom, the alkyl or virtue of (C1-C6)
Base；
The synthesis road of above-mentioned I type molecule is through as follows：
3,5 disubstituted (R in the ligand modified phenyl including 2 substitutionsdRd), 4 substitution (Re) and 3,4,5 three substitutions
(RdReRd) phenyl.The specific synthesis path of part is：By the Skraup ring-closing condensation reactions under amine ester exchange reaction, acid catalysis and
Hydroxyhalide reaction generates polysubstituted quinoline, then can obtain part by Suzuki coupling reactions.(chemistry as implied above
Equation) this path avoid alkyl suzuki coupling reaction and multiple reaction sites competition side reaction, can improve
Combined coefficient and reduction purification difficulty.The polysubstituted quinoline ligands that generation Ir is coordinated by quinoline part, diketone and Ir are miscellaneous
Method with thing is conventional method.
Above-mentioned Ra,Rb,RcRepresent H (either deuterium) atoms or (C1-C6) alkyl substituent is (related to take to aryl substituent
For base can by it is deuterated, substitute containing (C1-C6) alkyl or aryl substitutes).RdRepresent H atom or the substitution of (C1-C6) alkyl
Base. ReRepresentative represents H (either deuterium) atoms or (C1-C6) alkyl substituent and aryl substituent, and (related substituents can be by
It is deuterated, contain (C1-C6) alkyl substitution or aryl substitution) .Rf,RhRepresent (C1-C6) alkyl substituent and aryl substituent
(related substituents can by it is deuterated, substitute containing (C1-C6) alkyl or aryl substitutes).
In I type molecular formula, RfAnd Rh, it is separate, represents (C1-C6) alkyl chain generally, RfAnd Rh
It is consistent with each other.
In I type molecule, Ra,RbAnd RcIt is separate, represents a hydrogen atom, the alkyl or virtue of (C1-C6)
Base.
The iridium of above-mentioned poly-substituted quinoline coordination is miscellaneous also to have molecular formula 2, molecular formula 3, molecular formula 4, molecular formula with compound
5th, the structure of molecular formula 6 or molecular formula 7, its structural formula are as follows：
Each Ra,Rc,RdAnd ReIt can be individually present or be not present.Ra-c,Rd-eAnd Rf-gBetween independently of each other, respectively
Belong to its precursor group (quinoline, phenyl and diketone).Substituent on quinoline, 3,4,6-three substd quinolines represent Ra,Rb, Rc
All individualisms, 4,6-two substd quinolines represent Rb,RcIndividualism, 3,4-two substd quinolines represent Ra,RbIndividualism.
On the phenyl that quinoline is 2, RdAnd ReIt can be individually present or be not present.
The relation of substituent in molecular formula 2-7, its realm and definition are described as follows：
Molecular formula II:Ra-c、RfFor D-atom or (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-C6)
Alkyl substituent；
Molecular formula III:Rb-c、RfRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-
C6) alkyl substituent；
Molecular formula IV:Ra-b、RfRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-
C6) alkyl substituent；
Molecular formula V:Rb-c,Re,RfRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent；
Molecular formula VI:Ra-b、Re,RfRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent, RdRepresent
(C1-C6) alkyl substituent；
Molecular formula VII:Ra-c、Re-fRepresent D-atom or (C1-C6) alkyl substituent or aryl substituent:
According to above-mentioned to Ra-RhDefinition, the miscellaneous iridium of poly-substituted quinoline coordination with compound can be following structure：
The miscellaneous iridium with the coordination of compound 1- poly-substituted quinolines of iridium for being respectively designated as poly-substituted quinoline coordination miscellaneous matches somebody with somebody compound 225
The iridium being coordinated below with above-mentioned poly-substituted quinoline is miscellaneous with exemplified by compound 6,7,8,11,82,126,157,187,201
(hereinafter referred to as complex of iridium 6,7,8,11,82,126,157,187,201), the iridium of part poly-substituted quinoline coordination miscellaneous is matched somebody with somebody
The preparation method and its optical property of compound and the application as luminous organic material in terms of luminescent device are done specifically
It is bright
The preparation of the complex of iridium 11 of embodiment 1
Ra=p-methylphenyl, Rb=methyl, Rc=phenyl, Rd=methyl, Re=hydrogen, Rf=methyl
(1) synthesis of N- (4'- methyl-[1,1'- xenyls] -4- bases) -3- oxo -2- phenylbutanamides.100mL envelope
4'- methyl-[1,1'- biphenyl] -4- amine (1g, 5.5mmol), 2- phenylacetyls ethyl acetate (3.1g, 15mmol) are added in pipe
With dimethylbenzene (15 mL), reaction system N2After bubbling three divides, 145 DEG C are to slowly warm up to, and stirring 16 is small under the conditions of 145 DEG C
When.TLC (petroleum ethers：Ethyl acetate=5:1) display reaction is complete, reaction solution is cooled into room temperature, product separates out, filtering, air
Middle dry faint yellow N- (4'- methyl-[1,1'- xenyls] -4- bases) -3- oxo -2- phenylbutanamides (500mg, yield
26%).1H NMR (300MHz, DMSO) δ 10.40 (s, 1H), 7.66 (d, J=8.7Hz, 2H), 7.60 (d, J=8.7Hz,
2H), 7.53 (d, J=8.1 Hz, 2H), 7.38-7.31 (m, 5H), 7.24 (d, J=7.8Hz, 2H), 5.00 (s, 1H), 2.33
(s,3H),2.19(s,3H)。
(2) synthesis of 4- methyl -3- phenyl -6- (p-methylphenyl) quinoline -2- alcohol.N- is added in 100mL three-neck flasks
(4'- methyl-[1,1'- xenyls] -4- bases) -3- oxo -2- phenylbutanamides (500mg, 1.45mmol), nitrogen displacement is anti-
Bottle atmosphere is answered, the 3mL concentrated sulfuric acids are added dropwise to reaction system dropwise.Reaction system is heated to 50 DEG C, stirred 12 hours.TLC (stones
Oily ether：Ethyl acetate=1:1) display reaction is complete, and reaction solution is cooled into room temperature, is poured slowly into frozen water, and solid separates out, mistake
Filter, air drying obtain faint yellow 4- methyl -3- phenyl -6- (p-methylphenyl) quinoline -2- alcohol (320mg, yield 68%).1H
NMR (500 MHz, DMSO) δ 11.83 (s, 1H), 7.96 (s, 1H), 7.81 (d, J=8.5Hz, 1H), 7.64 (d, J=8.0Hz,
2H), 7.46-7.43 (m, 2H), 7.42-7.36 (m, 2H), 7.28 (d, J=7.5Hz, 2H), 7.26 (d, J=7.5Hz, 2H),
2.35(s, 3H),2.34(s,3H).
(3) synthesis of chloro- 4- methyl -3- phenyl -6- (p-methylphenyl) quinoline of 2-.4- is added in the neck round-bottom flasks of 50ml bis-
Methyl -3- phenyl -6- (p-methylphenyl) quinoline -2- alcohol (320mg, 1mmol), nitrogen displacement reaction bulb atmosphere, 3mL trichlorine oxygen
Phosphorus is added dropwise to reaction system dropwise.Reaction system is heated to 100 DEG C, stirred 18 hours.TLC (petroleum ethers：Ethyl acetate=1:
1) display reaction is complete, and reaction solution is cooled into room temperature, is poured slowly into frozen water, and solid separates out, and filters, washing, air drying
Obtain chloro- 4- methyl -3- phenyl -6- (p-methylphenyl) quinoline (300mg, 87%) of faint yellow 2-.1H NMR(300MHz,DMSO)
δ 8.32 (s, 1H), 8.16 (d, J=8.7Hz, 1H), 8.06 (d, J=8.7Hz, 1H), 7.80 (d, J=8.1Hz, 2H), 7.58-
7.49 (m,3H),7.37-7.34(m,4H),2.49(s,3H)2.39(s,3H).
(4) synthesis of 2- (3,5- 3,5-dimethylphenyls) -4- methyl -3- phenyl -6- (p- tolyl) quinoline.To 100mL's
Chloro- 4- methyl -3- phenyl -6- (p-methylphenyl) quinoline (300mg, 0.87mmol) of 2-, 3,5- diformazans are added in schlenk pipes
Phenyl boric acid (130.7 mg, 1.76mmol), three water potassium phosphates (703mg, 2.64mmol), 2- dicyclohexyl phosphine -2', 6'- diformazans
Epoxide biphenyl (28.9mg, 0.07mmol), three (dibenzalacetone) two palladium (16.1mg, 0.0176mmol) and toluene
(10mL), nitrogen displacement reaction bulb atmosphere.Reaction system is heated to 100 DEG C, stirred 12 hours.TLC (petroleum ethers：Acetic acid second
Ester=10:1) display reaction is complete, and reaction solution is diluted with ethyl acetate, and filtering, filtrate was spin-dried for post (petroleum ether：Ethyl acetate
=50:1) white 2- (3,5- 3,5-dimethylphenyls) -4- methyl -3- phenyl -6- (p- tolyl) quinoline (300mg, 70%) is obtained
。1H NMR(300MHz,CDCl3) δ 8.27-8.21 (m, 2H), 8.00 (dd, J=8.7,1.8Hz, 1H), 7.67 (d, J=
8.1Hz,2H),7.34–7.28(m,5H), 7.14–7.12(m,2H),6.92(s,2H),6.82(s,1H),2.58(s,3H),
2.44(s,3H),2.17(s,6H)
(5) synthesis of dimer 11.2- (3,5- 3,5-dimethylphenyls) -4- methyl -3- phenyl -6- is added into 15ml tube sealings
(p- tolyl) quinoline (82.6mg, 0.2mmol), three water iridous chlorides (14.1mg, 0.04mmol), ethylene glycol ethyl ether (3mL)
With water (1mL), nitrogen displacement reaction bulb atmosphere.Reaction system is heated to 100 DEG C, stirred 12 hours.Reaction solution is cooled to room
Temperature, solid separate out, and filter, and air drying obtains dimer 11 (30mg, 71%).
(6) synthesis of complex of iridium 11:The addition dimer 11 (100mg, 0.047mmol) into 15ml tube sealings, pentane -2,
4- diketone (0.1ml), sodium carbonate (32mg, 10mmol) and ethylene glycol ethyl ether (2mL), nitrogen displacement reaction bulb atmosphere, reactant
System is heated to reflux 12 hours.Reaction solution is cooled to room temperature, solid separates out, and filtering, solid crosses post (petroleum ether：Ethyl acetate=30:
1) complex of iridium 11 (80mg, 76%) of red is obtained.1H NMR(300MHz,CDCl3) δ 8.06 (d, J=1.5Hz, 2H),
7.93 (d, J=9.0Hz, 2H), 7.71-7.68 (m, 5H), 7.68-7.65 (m, 3H), 7.59-7.57 (m, 5H), 7.55-7.50
(m, 3H), 7.28 (d, J=9.0Hz, 4H), 6.39 (d, J=4.8Hz, 4H), 4.32 (s, 1H), 2.60 (s, 6H), 2.41 (s,
6H),1.93 (s,6H),1.42(s,6H),1.33(s,6H).MALDI-TOF MASS 1116.87[M+]Peak at
639nm, FWHM=62 nm in DCM；Peak at 639nm, FWHM=58nm in PMMA.
The preparation of the complex of iridium 126 of embodiment 2
Ra=methyl, Rb=p-methylphenyl, Rc=hydrogen, Rd=methyl, Re=hydrogen, Rf=methyl
(1) synthesis of 3- oxos-N, 3- bis--p- tolyl propionamide.To 100ml tube sealings add para-totuidine (2.7g,
25 mmol), 3- oxygen -3- p-methylphenyls-ethyl propionate (10.3g, 50mmol) and dimethylbenzene (20mL), reaction system N2Bubbling
After three points, 145 DEG C are to slowly warm up to, and stirred 16 hours under the conditions of 145 DEG C.TLC (petroleum ethers：Ethyl acetate=5:1) show
Show that reaction is complete, reaction solution is cooled to room temperature, product separates out, filtering, and air drying obtains white 3- oxos-N, 3- bis--p-
Tolyl propionamide (3.4g, 60%).1H NMR(300MHz,CDCl3) δ 9.21 (s, 1H), 7.94 (d, J=8.1Hz, 2H),
7.46 (d, J=7.5Hz, 2H), 7.31 (d, J=8.1Hz, 2H), 7.13 (d, J=7.5Hz, 2H), 4.07 (s, 1H), 4.04
(br,1H), 2.44(s,3H),2.32(s,3H).
(2) the synthesis of 6- methyl -4- (p-methylphenyl) quinoline -2- alcohol adds 3- oxo-N into 100mL three-neck flasks,
3- bis--p- tolyl propionamide (1g, 2.4mmol), nitrogen displacement reaction bulb atmosphere, the 3mL concentrated sulfuric acids are added dropwise to reaction dropwise
System.Reaction system is heated to 50 DEG C, stirred 12 hours.TLC (petroleum ethers：Ethyl acetate=3:1) display reaction is complete, will
Reaction solution is cooled to room temperature, is poured slowly into frozen water, and solid separates out, and filtering, air drying obtains white 6- methyl -4- (to first
Phenyl) quinoline -2- alcohol (800mg, 83%).1H NMR(300MHz,DMSO)δ11.74(s,1H),7.37-7.36(m,5H),
7.30 (d, J=8.4Hz, 1H), 7.18 (s, 1H), 6.32 (s, 1H), 2.41 (s, 3H), 2.26 (s, 3H)
(3) synthesis of chloro- 6- methyl -4- (p-methylphenyl) quinoline of 2-.Added into the neck round-bottom flasks of 50ml bis- 6- methyl-
4- (p-methylphenyl) quinoline -2- alcohol (499mg, 2mmol), nitrogen displacement reaction bulb atmosphere, 3.5mL POCl3s are added dropwise to dropwise
Reaction system.Reaction system is heated to 100 DEG C, stirred 18 hours.TLC (petroleum ethers：Ethyl acetate=6:1) display has been reacted
Entirely, reaction solution is cooled to room temperature, be poured slowly into frozen water, solid separates out, and filters, and washing, air drying obtains the 2- of white
Chloro- 6- methyl -4- (p-methylphenyl) quinoline (500mg, 87%).1H NMR (500MHz, DMSO) 7.93 (d, J=8.5Hz,
1H), 7.69 (d, J=8.5Hz, 1H), 7.63 (s, 1H), 7.46 (d, J=8.0Hz, 2H), 7.42-7.40 (m, 3H), 2.44
(s,3H), 2.43(s,3H).
(4) synthesis of 2- (3,5- 3,5-dimethylphenyls) -6- methyl -4- (p-methylphenyl) quinoline.Into 100ml round-bottomed flasks
Chloro- 6- methyl -4- (p-methylphenyl) quinoline (1g, 3.74mmmol) the 3,5- diformazans phenyl boric acids of addition 2- (1.12g,
7.48mmol), three water potassium phosphate (g, 14.96mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl (mg,
0.30mmol), three (dibenzalacetone) two palladium (mg, 0.075mmol) and toluene (10mL), nitrogen displacement reaction bulb atmosphere.
Reaction system is heated to 100 DEG C, stirred 12 hours.TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, reaction
Liquid is diluted with ethyl acetate, and filtering, filtrate was spin-dried for post (petroleum ether：Ethyl acetate=50:1) white 2- (3,5- dimethyl is obtained
Phenyl) -6- methyl -4- (p-methylphenyl) quinoline (1.0g, 79%).1H NMR(300MHz,CDCl3) δ 8.14 (d, J=8.4Hz,
1H), 7.78 (s, 2H), 7.75 (s, 1H), 7.67 (s, 1H), 7.56 (d, J=8.4Hz, 1H), 7.47 (d, J=7.8Hz,
2H), 7.37 (d, J=7.8Hz, 2H), 7.10 (s, 1H), 2.50 (s, 3H), 2.48 (s, 3H), 2.43 (s, 6H)
(5) synthesis of dimer 126.2- (3,5- 3,5-dimethylphenyls) -6- methyl -4- is added into 15ml tube sealings (to first
Phenyl) quinoline (64.4mg, 0.2mmol), three water iridous chlorides (14.1mg, 0.04mmol), ethylene glycol ethyl ether (3mL) and water
(1mL), nitrogen bubble three minutes, reaction system is heated to 120 DEG C, stirred 12 hours.Reaction solution is cooled to room temperature, solid analysis
Go out, filter, air drying obtains dimer 126 (25mg, 76%).
(6) synthesis of complex of iridium 126.The addition dimer 126 (166.2mg, 0.1mmol) into 75ml tube sealings, pentane-
2,4- diketone (40mg, 0.4mmol), sodium carbonate (53mg, 0.5mmol) and ethylene glycol ethyl ether (3mL), nitrogen bubble three minutes,
Reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, solid separates out, filtering, and ether washing, air drying obtains iridium
Complex 126.1H NMR (300MHz, DMSO) δ 7.90 (d, J=9.0Hz, 4H), 7.58 (s, 2H), 7.57-7.52 (m,
6H), 7.41 (d, J=7.8Hz, 4H), 7.14 (d, J=9.0Hz, 2H), 6.53 (s, 2H), 4.37 (s, 1H), 2.52 (s, 6H),
2.34 (s,12H),1.37(s,6H),1.34(s,6H).MS(MALDI-TOF):964.4[M]+Emission peak in
DCM at 626nm, FWHM=72nm, peak in PMMA at 625nm, FWHM=64nm.
The preparation method of the complex of iridium 201 of embodiment 3
Ra=methyl, Rb=p-methylphenyl, Rc=hydrogen, Rd=hydrogen, Re=methyl, Rf=methyl
(1) synthesis of dimer 201.6- methyl -2,4- bis--p- tolyl quinoline is added into 15ml tube sealings
(61.6mg, 0.2 mmol), three water iridous chlorides (14.1mg, 0.04mmol), ethylene glycol ethyl ether (3mL) and water (1mL), nitrogen
Bubbling three minutes, reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, solid separates out, filtering, air drying
Dimer 201 (25mg, 76%) is obtained, and is directly used in next step.
(2) synthesis of complex of iridium 201.The addition dimer (160.6mg, 0.1mmol) into 75ml tube sealings, pentane -2,
4- diketone (40mg, 0.4mmol), sodium carbonate (53mg, 0.5mmol) and ethylene glycol ethyl ether (3mL), nitrogen bubble three minutes, instead
System is answered to be heated to reflux 12 hours.Reaction solution is cooled to room temperature, solid separates out, filtering, and ether washing, air drying obtains iridium and matched somebody with somebody
Compound 201 (132mg, 71%).1H NMR (300MHz, DMSO) δ 8.32 (d, J=8.7Hz, 2H), 8.11 (s, 2H), 7.90
(d, J=8.1Hz, 2H), 7.65 (d, J=7.8Hz, 4H), 7.61 (s, 2H), 7.49 (d, J=8.1Hz, 4H), 7.37 (dd, J
=8.7,1.5Hz, 2H), 6.69 (d, J=8.1Hz, 2H), 6.20 (s, 2H), 4.71 (s, 1H), 2.51 (s, 6H), 2.39 (s,
6H),1.90 (s,6H),1.47(s,6H).MS MALDI-TOF 836.1[M-acac]+Peak in DCM solution at
RT at 611nm, FWHM 83nm, Peak in PMMA solution at RT at 609nm, FWHM 79nm.
The preparation of the complex of iridium 187 of embodiment 4
Ra=methyl, Rb=isobutyl group, Rc=methyl, Rd=methyl, Re=hydrogen, Rf=isobutyl group
(1) synthesis of 2,5- dimethyl -3- oxos-N- (p-methylphenyl) caproamide.Para-totuidine is added to 100ml tube sealings
(107.12m g, 1mmol), 2,5- dimethyl -3- oxo-hexanoic acid ethyl esters (346.4mg, 2mmol) and dimethylbenzene (2mL), reaction
System N2After bubbling three divides, 145 DEG C are to slowly warm up to, and stirred 16 hours under the conditions of 145 DEG C.TLC (petroleum ethers：Acetic acid second
Ester=5:1) display reaction is complete, reaction solution is cooled into room temperature, product separates out, and filtering, air drying obtains white 2,5- diformazans
Base -3- oxos-N- (p-methylphenyl) caproamide (120mg, 40%).1H NMR(300MHz,CDCl3)δ8.22(s,1H),7.39
(d, J=7.8Hz, 2H), 7.12 (d, J=7.8Hz, 2H), 3.54 (q, J=7.2Hz, 1H), 2.48 (d, J=6.9Hz, 2H),
2.31 (s, 3H), 2.22-2.14 (m, 1H), 1.49 (d, J=6.9Hz, 3H), 0.94-0.91 (m, 6H)
(2) synthesis of 4- isobutyl groups -3,6- dimethyl quinoline -2- alcohol.Added into 100mL three-neck flasks 2,5- dimethyl-
3- oxos-N- (p-methylphenyl) caproamide (1g, 4mmol), nitrogen displacement reaction bulb atmosphere, the 3.5mL concentrated sulfuric acids are added dropwise to dropwise
Reaction system.Reaction system is heated to 50 DEG C, stirred 12 hours.TLC (petroleum ethers：Ethyl acetate=3:1) display has been reacted
Entirely, reaction solution is cooled to room temperature, be poured slowly into frozen water, solid separates out, and filtering, air drying obtains faint yellow 4- isobutyls
Base -3,6- dimethyl quinoline -2- alcohol (830mg, 90%).1H NMR(300MHz,CDCl3)δ11.55(s,1H),7.50(s,1H),
7.25-7.17 (m, 2H), 2.78 (d, J=7.2Hz, 2H), 2.36 (s, 3H), 2.11 (s, 3H), 1.98-1.89 (m, 1H),
0.95 (d, J=6.6Hz, 6H).
(3) synthesis of the chloro- 4- isobutyl groups -3,6- dimethyl quinolines of 2-.4- isobutyls are added into the neck round-bottom flasks of 50ml bis-
Base -3,6- dimethyl quinoline -2- alcohol (800mg, 3.5mmol), nitrogen displacement reaction bulb atmosphere, 3.5mL POCl3s are added dropwise dropwise
Enter reaction system.Reaction system is heated to 100 DEG C, stirred 18 hours.TLC (petroleum ethers：Ethyl acetate=5:1) display reaction
Completely, reaction solution is cooled to room temperature, be poured slowly into frozen water, solid separates out, and filters, and washing, air drying obtains faint yellow
The chloro- 4- isobutyl groups -3,6- dimethyl quinolines of 2- (830mg, 93%).1H NMR(300MHz,DMSO)δ7.89(s,1H),7.79
(d, J=8.4Hz, 1H), 7.56 (d, J=8.4Hz, 1H), 3.05 (d, J=7.2Hz, 2H), 2.53 (s, 3H), 2.49 (s,
3H), 2.02-1.93 (m, 1H), 0.94 (d, J=6.6Hz, 6H)
(4) synthesis of 2- (3,5- 3,5-dimethylphenyls) -4- isobutyl group -3,6- dimethyl quinolines.To 100mL schlenk
Addition chloro- 4- isobutyl groups -3, the 6- dimethyl quinolines (800mg, 3.23mmol) of 2- in pipe, 3,5- diformazan phenyl boric acids (969.6mg,
6.46mmol), three water potassium phosphate (4.3g, 16.15mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl (106.1mg,
0.26mmol), three (dibenzalacetone) two palladium (59mg, 0.065mmol) and toluene (10mL), nitrogen displacement reaction bulb atmosphere
Enclose.Reaction system is heated to 100 DEG C, stirred 12 hours.TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, instead
Answer liquid to be diluted with ethyl acetate, filter, filtrate was spin-dried for post (petroleum ether：Ethyl acetate=10:1) white 2- (3,5- diformazans are obtained
Base phenyl) -4- isobutyl group -3,6- dimethyl quinolines (700mg, 55%).1H NMR(500MHz,CDCl3)δ8.02(s,1H),
7.76 (s, 1H), 7.46 (d, J=8.0Hz, 1H), 7.10 (s, 2H), 7.05 (s, 1H), 3.05 (d, J=7.5Hz, 2H),
2.57 (s, 3H), 2.38 (s, 6H), 2.37 (s, 3H), 2.15-2.13 (m, 1H), 1.04 (d, J=6.5Hz, 6H)
(5) synthesis of dimer 187.2- (3,5- 3,5-dimethylphenyls) -4- isobutyl groups -3,6- two is added into 15ml tube sealings
Methylquinoline (65.4mg, 0.2mmol), three water iridous chlorides (14.1mg, 0.04mmol), ethylene glycol ethyl ether (3mL) and water
(1mL), nitrogen displacement reaction bulb atmosphere, reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, solid separates out,
Filtering, air drying obtain dimer 187 (30mg, 87%).
(6) synthesis of complex of iridium 187.The addition dimer 187 (250mg) into 15ml tube sealings, 2,8- dimethylnonanes-
4,6- diketone (0.1ml), sodium carbonate (32mg, 10mmol) and ethylene glycol ethyl ether (2mL), nitrogen displacement reaction bulb atmosphere, reaction
System is heated to reflux 12 hours.Reaction solution is cooled to room temperature, solution was spin-dried for post (petroleum ether：Ethyl acetate=50:1) obtain red
The complex of iridium 187 of color.1H NMR(500MHz,CDCl3) δ 7.74 (d, J=8.5Hz, 2H), 7.62 (s, 2H), 7.56 (s,
2H), 7.02 (d, J=8.5Hz, 2H), 6.52 (s, 2H), 4.08 (s, 1H), 3.16-3.06 (m, 4H), 3.01 (s, 6H),
2.96-2.92(m, 2H),2.41(s,6H),2.35(s,6H),2.23–2.20(m,2H),1.57-1.55(m,2H),1.51–
1.49 (m, 2H), 1.24 (s, 6H), 1.10 (d, J=6.5Hz, 6H), 1.08 (d, J=6.5Hz, 6H), 0.47 (d, J=
6.5Hz, 6H), 0.23 (d, J=6.5Hz, 6H) .MS (MALDI-TOF):1007.9[M-1]+Peak in DCM at room
Temperature at 617nm, FWHM=68 nm.Peak in PMMAat room temperature at 618nm,
FWHM=68nm.
The synthesis of the complex of iridium 82 of embodiment 5
Ra=p-methylphenyl, Rb=isobutyl group, Rc=hydrogen, Rd=hydrogen, Re=methyl, Rf=isobutyl group
(1) synthesis of 5- methyl-N- (4'- methyl-[1,1'- xenyls] -4- bases) -3- oxohexanoyl amine.1000mL's
4'- methyl-[1,1'- biphenyl] -4- amine (52.6g, 287mmol), 5- methyl -3- oxo caproic acid second are added in three neck round bottom
Ester (59.3g, 344 mmol) and dimethylbenzene (450mL), reaction system N2After bubbling three divides, 145 DEG C are to slowly warm up to, and
3-4 hours are stirred under the conditions of 145 DEG C.TLC (petroleum ethers：Ethyl acetate=5:1) display reaction is complete, and reaction solution is cooled into room
Temperature, product separate out, and filtering, air drying obtains faint yellow 5- methyl-N- (4'- methyl-[1,1'- xenyl] -4- bases) -3- oxygen
For caproamide (46.1 g, 52%).1H NMR(300MHz,DMSO)δ10.13(s,1H),7.66-7.58(m,4H),7.53(d,
J=8.1Hz, 2H), 7.25 (d, J=8.1Hz, 2H), 3.53 (s, 2H), 2.46 (d, J=6.9Hz, 2H), 2.33 (s, 3H),
2.11-2.02 (m, 1H), 0.89 (d, J=6.6Hz, 6H)
(2) synthesis of 4- isobutyl groups -6- (p-methylphenyl) quinoline -2- alcohol.5- first is added into 250ml three neck round bottom
Base-N- (4'- methyl-[1,1'- xenyl] -4- bases) -3- oxohexanoyls amine (18.3g, 59.1mmol), nitrogen displacement reaction
Atmosphere, the 50mL concentrated sulfuric acids are added dropwise to reaction system dropwise, and reaction system is heated into 40-50 DEG C, stirred 12 hours.TLC (stones
Oily ether：Ethyl acetate=3:1) display reaction is complete, and reaction solution is cooled into room temperature, is poured slowly into frozen water, and solid separates out, mistake
Filter, washing, air drying obtain white 4- isobutyl groups -6- (p-methylphenyl) quinoline -2- alcohol (15.5g, 95%).1H NMR
(500MHz,CDCl3) δ 9.16 (s, 0.8H, enol), 7.60 (d, J=8.5Hz, 2H), 7.54 (d, J=8.5Hz, 2H),
7.46 (d, J=8.0Hz, 2H), 7.23 (d, J=8.0Hz, 2H), 3.56 (s, 2H), 2.47 (d, J=6.8Hz, 2H), 2.38
(s, 3H), 2.20 (th, J=6.8,6.6Hz；1H), 2.06 (s, 0.2H), 0.97 (d, J=6.6Hz, 6H)
(3) synthesis of chloro- 4- isobutyl groups -6- (p-methylphenyl) quinoline of 2-.It is different that 4- is added into 500ml three neck round bottom
Butyl -6- (p-methylphenyl) quinoline -2- alcohol (1g, 3.6mmol), nitrogen displacement reaction atmosphere, 3mL POCl3s are added dropwise dropwise
Enter reaction system, reaction system is to slowly warm up to 100 DEG C, stirred 18 hours.TLC (petroleum ethers：Ethyl acetate=6:1) show
Reaction is complete, and reaction solution is cooled into room temperature, is poured slowly into frozen water, and solid separates out, and filters, and washing, air drying obtains deep yellow
Chloro- 4- isobutyl groups -6- (p-methylphenyl) quinoline (1g, 94%) of color 2-.1H NMR(400MHz,CDCl3) δ 8.09 (d, J=2.0,
1H), 8.06 (d, J=5.3Hz, 1H), 7.94 (dd, J=10.2,2.0Hz, 1H), 7.58 (d, J=8.1Hz, 2H), 7.33 (d,
J=8.1Hz, 2H), 7.22 (s, 1H), 2.94 (d, J=7.3Hz, 2H), 2.44 (s, 3H), 2.35-2.05 (m, 1H), 1.02
(d, J=6.6 Hz, 6H)
(4) the synthesis of 2- (4- aminomethyl phenyls) -4- isobutyl groups -6- (p-methylphenyl) quinoline adds into 500ml round-bottomed flasks
Enter chloro- 4- isobutyl groups -6- (p-methylphenyl) quinoline (4.8g, 15.5mmol) of 2-, to methylphenylboronic acid (4.2g g, 31mmol),
Three water potassium phosphates (20.6g, 77.5mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyls (509mg, 1.24mmol), three
(dibenzalacetone) two palladium (284mg, 0.31mmol) and toluene (110mL), nitrogen displacement reaction atmosphere, reaction solution are heated
Backflow 12 hours.TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, and reaction solution is diluted with ethyl acetate, filtering,
Filtrate was spin-dried for post (petroleum ether：Ethyl acetate=10:1) white 2- (4- aminomethyl phenyls) -4- isobutyl groups -6- (p-methylphenyl) is obtained
Quinoline (4g, 71%).
(5) it is (right to add 2- (4- aminomethyl phenyls) -4- isobutyl groups -6- into 100ml round-bottomed flasks by the synthesis of dimer 82
Tolyl) quinoline (1.1g, 3mmol), three water iridous chlorides (195mg, 0.6mmol), ethylene glycol ethyl ether (15mL) and water
(5mL), nitrogen displacement reaction bulb atmosphere.Reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, solid separates out,
Filtering, ether (8mL × 3) washing, air drying obtain dimer 82 (500mg, 87%).
(6) synthesis of complex of iridium 82.The addition dimer (650mg, 0.34mmol) into 100ml round-bottomed flasks, 2,8-
Dimethylnonane -4,6- diketone (304mg, 1.65mmol), sodium carbonate (350mg, 3.3mmol) and ethylene glycol ethyl ether (20mL),
Nitrogen displacement reaction bulb atmosphere, reaction system are heated to reflux 12 hours.Reaction solution is cooled to room temperature, was spin-dried for post (petroleum ether：Two
Chloromethanes=1:1) complex of iridium 82 (740mg, 99%) of red is obtained.1H NMR(400MHz,CDCl3) δ 8.49 (d, J=
9.1Hz, 2H), 8.05 (d, J=2.0Hz, 2H), 7.84 (s, 2H), 7.73 (d, J=8.1Hz, 2H), 7.58 (dd, 9.1,2Hz,
2H), 7.57 (dd, 8.0Hz, 4H), 7.29 (d, J=8.0Hz, 4H), 6.77 (d, J=8.1Hz, 2H), 6.45 (s, 2H), 4.57
(s, 1H), 3.25 (dd, J=13.5,6.3Hz, 2H), 2.99 (dd, J=13.5,7.7Hz, 2H), 2.42 (s, 6H), 2.28-
2.22 (m, 2H), 1.99 (s, 6H), 1.74 (dd, J=12.2,5.4Hz, 2H), 1.45 (dd, J=12.4,8.9Hz, 2H),
1.33 (m, 2H), 1.17 (d, J=6.6Hz, 6H), 1.10 (d, J=6.5Hz, 6H), 0.45 (d, J=6.6Hz, 6H), 0.05
(d, J=6.5Hz, 6H) .Peak at 596nm, FWHM=71nm in DCM；Peak at 596nm, FWHM=67nm in
PMMA
The complex of embodiment 6 (DMPQ-TBH) 2Ir (divm) synthesis
Ra=p-methylphenyl, Rb=isobutyl group, Rc=hydrogen, Rd=methyl, Re=hydrogen, Rf=isobutyl group patent
WO2016072780 reports the complex
(1) synthesis of 2- (3,5- aminomethyl phenyl) -4- isobutyl groups -6- (p-methylphenyl) quinoline.Into 500ml round-bottomed flasks
Addition chloro- 4- isobutyl groups -6- (p-methylphenyl) quinoline (22.3g, 60mmol) of 2-, 1,3- dimethylphenyl boronic acid (18g,
120mmol), three water potassium phosphate (80g, 300mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl (1.97g,
4.8mmol), three (dibenzalacetone) two palladium (1.1g, 1.2mmol) and toluene (300mL), nitrogen displacement reaction atmosphere will
Reaction solution is heated to reflux 12 hours.TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, reaction solution ethyl acetate
Dilution, filtering, filtrate were spin-dried for post (petroleum ether：Ethyl acetate=10:1) white 2- (3,5- 3,5-dimethylphenyls) -4- isobutyls are obtained
Base -6- (p-methylphenyl) quinoline (17.3g, 76%).1H NMR(400MHz,CDCl3) δ 8.23 (d, J=8.4Hz, 1H), 8.14
(d, J=2.0Hz, 1H), 7.95 (dd, J=8.4,2.0Hz, 1H), 7.76 (s, 2H), 7.66 (s, 1H), 7.63 (d, J=
8.0Hz, 2H), 7.33 (d, J=8.0Hz, 2H), 7.11 (s, 1H), 3.03 (d, J=7.2Hz, 2H), 2.45 (s, 9H), 2.19
(ht, J=7.2,6.7Hz, 1H), 1.58 (s, 6H), 1.04 (d, J=6.7Hz, 6H)
(2) the synthesis of dimer adds 2- (3,5- 3,5-dimethylphenyls) -4- isobutyl groups -6- into 100ml round-bottomed flasks
(p-methylphenyl) quinoline (1.9g, 4.0mmol), three water iridous chlorides (0.353g, 1.0mmol), ethylene glycol ethyl ether (15mL) and
Water (5mL), nitrogen displacement reaction bulb atmosphere.Reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, solid analysis
Go out, filter, ether (8mL × 3) washing, air drying obtains dimer (2.3g)..
(3) complex (DMPQ-TBH)2Ir (divm) synthesis.Into 100ml round-bottomed flasks add dimer (2.3g,
1.17 mmol), 2,8- dimethylnonane -4,6- diketone (1.2mL, 5.85mmol), sodium carbonate (1.24g, 11.7mmol) and second
Glycol ether (20mL), nitrogen displacement reaction bulb atmosphere, reaction system are heated to reflux 12 hours.Reaction solution is cooled to room temperature, revolved
Did post (petroleum ether：Dichloromethane=1:1) complex (DMPQ-TBH) of red is obtained2Ir (divm) (3.0g, 85%).1H
NMR (400MHz,CDCl3) δ 8.04-7.96 (m, 4H), 7.86 (s, 2H), 7.61 (s, 2H), 7.53 (d, J=7.9Hz, 4H),
7.52 (m, 2H), 7.27 (d, J=7.9Hz, 4H), 6.52 (s, 2H), 4.27 (s, 1H), 3.13-2.95 (m, 4H), 2.40
(s,6H),2.38(s,6H),2.33-2.16(m,2H),1.52-1.60(m,2H),1.43-1.52(m,2H),1.24-1.36
(m, 2H), 1. 12 (d, J=5.1Hz, 12H), 0.51 (d, J=6.5Hz, 6H), 0.18 (d, J=6.4Hz, 6H) .MS
(MALDI-TOF):1133.5 [M]+Peak at 615nm, FWHM=58nm in DCM；Peak at 623nm, FWHM=
68nm in PMMA
The synthesis of the complex of iridium 157 of embodiment 7
Ra=p-methylphenyl, Rb=isobutyl group, Rc=hydrogen, Rd=methyl, Re=methyl, Rf=isobutyl group
(1) synthesis of dimer 157.4- isobutyl groups -6- (p- tolyl) -2- (3,4,5- tri- are added into 15ml tube sealings
Aminomethyl phenyl) quinoline (393.3mg, 1.0mmol), three water iridous chlorides (65.5mg, 0.2mmol), ethylene glycol ethyl ether (3mL)
With water (1mL), nitrogen displacement reaction bulb atmosphere, reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, solid analysis
Go out, filter, air drying obtains dimer 157 (155mg, 77%).
(2) synthesis of complex of iridium 157.Dimer (202.5mg, 0.1mmol), 2,8- diformazans are added into 15ml tube sealings
Base nonane -4,6- diketone (0.1ml), sodium carbonate (53mg, 0.5mmol) and ethylene glycol ethyl ether (3mL), nitrogen displacement reaction bulb atmosphere
Enclose, reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, is spin-dried for, crosses post (petroleum ether：Ethyl acetate=30:1)
To the complex of iridium 157 (155mg, 67%) of red.1H NMR(300MHz,CDCl3) δ 7.97 (d, J=1.8Hz, 2H), 7.88
(s, 1H), 7.84 (d, J=6.6Hz, 3H), 7.63 (s, 2H), 7.57-7.54 (m, 3H), 7.52-7.51 (m, 3H), 7.48 (d,
J=2.1 Hz, 1H), 7.28-7.25 (m, 3H), 4.25 (s, 1H), 3.03 (d, J=6.9Hz, 4H), 2.40 (s, 12H),
2.31-2.14(m,4H), 2.13(s,0H),2.01(s,6H),1.57-1.55(m,2H),1.50-1.51(m,2H),1.35
(s, 6H), 1.26 (s, 1H), 1.14-1.11 (m, 12H), 0.52 (d, J=6.3Hz, 6H), 0.22 (d, J=6.3Hz, 6H)
.MS(MALDI-TOF):1160.6[M]+Peak in DCM at room temperature at 610nm, FWHM=58nm,
Peak in PMMA at room temperature at 609nm, FWHM=51nm.
The synthesis of the complex of iridium 6 of embodiment 8
Ra=p-methylphenyl, Rb=isobutyl group, Rc=methyl, Rd=methyl, Re=hydrogen, Rf=methyl
(1) synthesis of 2,5- dimethyl-N -s (4'- methyl-[1,1'- xenyls] -4- bases) -3- oxohexanoyl amine.To
4'- methyl-[1,1'- biphenyl] -4- amine (183mg, 1.0mmol), 2,5- dimethyl -3- oxo caproic acids are added in 100ml tube sealings
Ethyl ester (346.4mg, 2 mmol) and dimethylbenzene (2mL), reaction system N2After bubbling three divides, 145 DEG C are to slowly warm up to, and
Stirred 16 hours under the conditions of 145 DEG C.TLC (petroleum ethers：Ethyl acetate=5:1) display reaction is complete, and reaction solution is cooled into room temperature,
Product separates out, and filtering, air drying obtains faint yellow 2,5- dimethyl-N -s (4'- methyl-[1,1'- xenyl] -4- bases) -3-
Oxohexanoyl amine (198 mg, 47%).1H NMR (300MHz, DMSO) δ 10.23 (s, 1H), 7.67 (d, J=8.7Hz, 2H),
7.60 (d, J=8.7Hz, 2H), 7.53 (d, J=8.1Hz, 2H), 7.25 (d, J=8.1Hz, 2H), 3.66 (q, J=6.9Hz,
1H), 2.45 (t, J=6.6Hz, 2H), 2.33 (s, 3H), 2.12-1.98 (m, 1H), 1.24 (d, J=6.9Hz, 3H), 0.85
(t, J=6.6Hz, 6H)
(2) synthesis of 4- isobutyl groups -3- methyl -6- (p-methylphenyl) quinoline -2- alcohol.Added into 100mL three-neck flasks
2,5- dimethyl-N -s (4'- methyl-[1,1'- xenyls] -4- bases) -3- oxohexanoyls amine (1.61g, 5mmol), nitrogen displacement
Reaction bulb atmosphere, the 9mL concentrated sulfuric acids are added dropwise to reaction system dropwise.Reaction system is heated to 50 DEG C, stirred 12 hours.TLC
(petroleum ether：Ethyl acetate=3:1) display reaction is complete, and reaction solution is cooled into room temperature, is poured slowly into frozen water, and solid separates out,
Filtering, air drying obtain yellow 4- isobutyl group -3- methyl -6- (p-methylphenyl) quinoline -2- alcohol (1.3g, 86%).1H
NMR(300MHz, CDCl3) δ 11.69 (s, 1H), 7.86 (s, 1H), 7.71 (d, J=8.4Hz, 1H), 7.57 (d, J=
8.1Hz, 2H), 7.36 (d, J=8.4Hz, 1H), 7.25 (d, J=8.1Hz, 2H), 2.89 (d, J=7.2Hz, 2H), 2.35
(s, 3H), 2.15 (s, 3H), 2.01-1.94 (m, 1H), 0.98 (d, J=6.6Hz, 6H)
(3) synthesis of chloro- 4- isobutyl groups -3- methyl -6- (p-methylphenyl) quinoline of 2-.Into 100ml three neck round bottom
Add 4- isobutyl group -3- methyl -6- (p-methylphenyl) quinoline -2- alcohol (1g, 3.3mmol), nitrogen displacement reaction bulb atmosphere, 6mL
POCl3 is added dropwise to reaction system dropwise.Reaction system is heated to 100 DEG C, stirred 18 hours.TLC (petroleum ethers：Acetic acid second
Ester=6:1) display reaction is complete, and reaction solution is cooled into room temperature, is poured slowly into frozen water, and solid separates out, and filters, washing, air
In be dried to obtain chloro- 4- isobutyl groups -3- methyl -6- (p-methylphenyl) quinoline (950mg, 90%) of yellow 2-.
The synthesis of 2- (3,5- 3,5-dimethylphenyls) -4- isobutyl group -3- methyl -6- (p- tolyl) quinoline.To 100mL's
Chloro- 4- isobutyl groups -3- methyl -6- (p-methylphenyl) quinoline (900mg, 2.8mmol) of 2-, 3,5- diformazans are added in schlenk pipes
Phenyl boric acid (836.5 mg, 5.6mmol), three water potassium phosphates (3.73g, 14mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxys
Biphenyl (91.9mg, 0.224 mmol), three (dibenzalacetone) two palladium (51.3mg, 0.056mmol) and toluene (10mL), nitrogen
Gas replaces reaction bulb atmosphere.Reaction system is heated to 100 DEG C, stirred 12 hours.TLC (petroleum ethers：Ethyl acetate=10:1)
Display reaction is complete, and reaction solution is diluted with ethyl acetate, and filtering, filtrate was spin-dried for post (petroleum ether：Ethyl acetate=50:1)
White 2- (3,5- 3,5-dimethylphenyls) -4- isobutyl group -3- methyl -6- (p- tolyl) quinoline (770mg, 70%).1H NMR
(300MHz,CDCl3) δ 8.14 (s, 1H), 8.13 (s, 1H), 7.86 (d, J=8.1Hz, 1H), 7.59 (d, J=7.8Hz,
2H), 7.30 (d, J=7.8Hz, 2H), 7.23 (s, 1H), 7.10 (s, 2H), 7.04 (s, 1H), 3.09 (d, J=7.2Hz,
2H), 2.41 (s, 3H), 2.37 (s, 9H), 2.22-2.10 (m, 1H), 1.04 (d, J=6.6Hz, 6H)
(4) synthesis of dimer 6.Added into 15ml tube sealings 2- (3,5- 3,5-dimethylphenyls) -4- isobutyl group -3- methyl -
6- (p- tolyl) quinoline (393.2mg, 1mmol), three water iridous chlorides (70.5mg, 0.2mmol), ethylene glycol ethyl ether
(3mL) and water (1mL), nitrogen displacement reaction bulb atmosphere.Reaction system is heated to 100 DEG C, stirred 12 hours.Reaction solution is cold
To room temperature, solid separates out, filtering, and ether washing, air drying obtains dimer 6 (180mg, 89%).
(5) synthesis of complex of iridium 6.Dimer 6 (202.5mg, 0.1mmol), pentane -2,4- are added into 15ml tube sealings
Diketone (0.1 ml), sodium carbonate (53mg, 0.5mmol) and ethylene glycol ethyl ether (3mL), nitrogen displacement reaction bulb atmosphere, reactant
System is heated to reflux 12 hours.Reaction solution is cooled to room temperature, is spin-dried for, crosses post (petroleum ether：Ethyl acetate=30:1) red is obtained
Complex of iridium 6 (150mg, 70%).1H NMR (300MHz, DMSO) δ 7.96 (s, 2H), 7.84 (d, J=9.0Hz, 2H),
7.62 (s, 2H), 7.50-7.47 (m, 6H), 7.24 (m, J=7.5Hz, 4H), 6.55 (s, 2H), 4.11 (s, 1H), 3.20-
3.08 (m, 4H), 3.04 (s, 6H), 2.36 (d, J=8.9Hz, 12H), 2.18 (m, 1H), 2.00 (m, 1H), 1.31 (s, 6H),
1.17 (s, 6H), 1.09 (d, J=6.6 Hz, 6H), 0.97 (d, J=6.6Hz, 6H) .MS (MALDI-TOF):1074.4[M-2
]+Peak in DCM at room temperature at 631nm, FWHM=70nm, Peak in PMMA at room
Temperature at 630nm, FWHM=62 nm.
The synthesis of the complex of iridium 7 of embodiment 9
Ra=p-methylphenyl, Rb=isobutyl group, Rc=methyl, Rd=methyl, Re=hydrogen, Rf=isobutyl group
Above-mentioned dimer (202.5mg, 0.1mmol), 2,8- dimethylnonane -4,6- diketone are added into 15ml tube sealings
(0.1ml), sodium carbonate (53mg, 0.5mmol) and ethylene glycol ethyl ether (3mL), nitrogen displacement reaction bulb atmosphere, reaction system heating
Backflow 12 hours.Reaction solution is cooled to room temperature, is spin-dried for, crosses post (petroleum ether：Ethyl acetate=15:1) iridium for obtaining red coordinates
Thing 7 (155 mg, 72%).1H NMR (300MHz, DMSO) δ 7.99 (d, J=1.5Hz, 2H), 7.89 (d, J=9.0Hz, 2H),
7.67 (s, 2H), 7.51-7.50 (m, 4H), 7.50-7.46 (m, 2H), 7.27 (d, J=7.8Hz, 4H), 6.57 (s, 2H),
4.12(s,1H),3.19 –2.98(m,4H),3.05(s,6H),2.40(s,6H),2.38(s,6H),2.31–2.24(m,2H),
1.62-1.54 (m, 2H), 1.42-1.36 (m, 2H), 1.30 (s, 6H), 1.36-1.20 (m, 2H), 1.18-1.11 (m, 12H),
0.47 (d, J=6.6Hz, 6H), 0.26 (d, J=6.6Hz, 6H).MS(MALDI-TOF):1160.6[M]+Peak in DCM
At room temperature at 629nm, FWHM=66nm, Peak in PMMA at room temperature at
630nm, FWHM=60nm.
The synthesis of the complex of iridium 8 of embodiment 10
Ra=p-methylphenyl, Rb=isobutyl group, Rc=methyl, Rd=methyl, Re=hydrogen, Rf=isopropyl
Above-mentioned dimer (202.5mg 0.1mmol), 2,6- dimethyl heptane -3,5- diketone are added into 15ml tube sealings
(0.1ml), sodium carbonate (53mg, 0.5mmol) and ethylene glycol ethyl ether (3mL), nitrogen displacement reaction bulb atmosphere, reaction system add
Heat backflow 12 hours.Reaction solution is cooled to room temperature, is spin-dried for, crosses post (petroleum ether：Ethyl acetate=15:1) iridium for obtaining red is matched somebody with somebody
Compound 8 (153mg, 71%).1H NMR (300MHz, DMSO) δ 8.14 (s, 2H), 7.79 (d, J=9.3Hz, 2H), 7.71 (s,
2H), 7.65 (s, 2H), 7.62-7.59 (m, 4H), 7.29 (d, J=8.1Hz, 4H), 6.45 (s, 2H), 4.26 (s, 1H),
3.18(s,4H),3.03(s,6H), 2.35(s,6H),2.31(s,6H),2.21-2.11(m,2H),1.77-1.66(m,2H),
1.13 (s, 6H), 1.08-1.05 (m, 12H), 0.61 (d, J=6.6Hz, 6H), 0.41 (d, J=6.6Hz, 6H) .MS
(MALDI-TOF):1131.9[M-1]+Peak in DCM at room temperature at 630nm, FWHM=63nm,
Peak in PMMA at room temperature at 631nm, FWHM=59nm.
The complex of iridium 6,7,8,11,82,126,157,187,201 of embodiment 11 is used as phosphorescent light-emitting materials and conventional phosphor
Comparison of the red light material in terms of optical property
Respectively to complex of iridium 6,7,8,11,82,126,157,187,201 of the present invention as phosphorescent light-emitting materials with
Conventional phosphor red light material Ir (PQ)2(acac)、Ir(DMPQ)2And (DMPQ-TBH) (acac)2Ir (divm) optical properties of materials
It is as follows to be compared method of testing：The band gap magnitude (Eg) and LUMO values of material are measured using cyclic voltammetry (CV).Whole test
Process is carried out on the CHI600D electrochemical workstations (Shanghai Chen Hua instrument company) in glove box (Lab2000, Etelux),
Using Pt posts as working electrode, using Ag/AgCl as reference electrode, Pt silks are that auxiliary electrode forms three-electrode system, and test process adopts
Medium is 0.1M hexafluorophosphoric acid 4-butyl amines (Bu4NPF6) dimethyl amide (DMF) solution, survey potential to add
The ferrocene (Fc) entered is used as internal standard.The HOMO values of material pass through Model IPS-4 Ionization Energy
Measurement System directly tests obtain.The fluorescence quantum efficiency (PLQE) of material is according to formula
(wherein：ΦsIt is the fluorescence quantum yield of sample, ΦrIt is the fluorescence quantum yield of standard specimen, η is the refractive index of solution, AsAnd ArIt is
Absorption value at the fluorescence exciting wavelength of sample and standard specimen, ΙsAnd ΙrIt is the fluorescence integral area of sample and standard specimen) use relative method
It is calculated.The mark thing of material and known quantum yield is configured to the polymethyl methacrylate (PMMA) of same concentrations
Chloroform soln, spin-coating film, under the same measuring conditions, measure ultra-violet absorption spectrum (GENESYS 10S, Thermo)
With fluorescence spectrum (F97pro sepectrophotofluorometers, rib light science and technology).The photon energy (ET1) of material by formula E=h ν=
1240/ λ (wherein λ is the tangent line wavelength of the fluorescence spectrum original position of material PMMA film) is calculated.)
A is measured by cyclic voltammetric
The energy of b triplet states
C PLQE efficiency is with Ir (PQ)2(acac) one unit of value on the basis of the luminous efficiency under 298K.
The embodiment of the present invention can obtain following characteristics with the example contrast with announcement in upper table：With Ir (DMPQ)2
(acac) on the basis of the emission wavelength in PMMA and efficiency, the Ir complexs of 4,6 substitutions of quinoline can make spectral red shift
PLQE in 30nm, PMMA film improves about 20%.It is red that the Ir complexs of 3,4,6 substitutions of quinoline can continue luminescent spectrum
Move about 7nm.The part of substituent is introduced in the contraposition of the phenyl of 2 substitutions of quinoline can increase substantially fluorescence quantum efficiency,
Such as complex of iridium 82,157, spectrum has 14-27nm blue shift.Film PLQE highests be the substitution of 4,6, quinoline and phenyl 3,4,
The Ir of 5 substitutions miscellaneous complex.Understand that above-mentioned complex of iridium may be used as red light material by Eg (band gap magnitude) comparison, use
Lighted as display material, feux rouges saturation degree is very high.
The complex of iridium 6,7,8,11,82,126,157,187,201 of embodiment 12 is used as phosphorescent light-emitting materials and conventional phosphor
Red light material is applied to the comparison after device
Above-mentioned complex of iridium 6,7,8,82,187 is as phosphorescent light-emitting materials and conventional phosphor red light material Ir (PQ)2
And Ir (DMPQ) (acac)2(acac) device comparison is carried out, design OLED structure is as follows：ITO/HAT-CN(10nm)/
TAPC(40 nm)/NPB:red dopant(95:5,20nm)/Balq(10nm)/Bphen(50nm)/Liq(1nm)/Al。
Crucible equipped with OLED organic materials and the crucible equipped with metal aluminum shot are placed sequentially in organic evaporating source and nothing
On machine evaporation source position.Cavity is closed, just vacuumize and pumping high vacuum step so that evaporation degree inside OLED evaporated devices
Reach 10E-7Torr.
OLED evaporation film-formings：OLED organic evaporatings source is opened, 100 DEG C of preheatings, preheating time are carried out to OLED organic materials
For 15 minutes, ensure further to remove the steam in OLED organic materials.Then the organic material that needs are deposited is carried out quick
Heating is heated, and opens the baffle plate above evaporation source, until the evaporation source of the material has organic material to run out of, while crystal oscillator
When piece detector detects evaporation rate, then slowly heated up, increasing extent of temperature is 1~5 DEG C, until evaporation rate stabilization exists
During the 1A/ seconds, the baffle plate immediately below mask plate plate is opened, OLED film forming is carried out, the organic film on ito substrate is observed when computer end
When reaching default thickness, baffle plate directly over mask plate baffle plate and evaporation source is closed, closes the evaporation source heater of the organic material.
The evaporation process of other organic material and cathodic metal materials is as described above.Encapsulation carries out photocuring envelope using UV epoxy resin
Dress.Sample after encapsulation carries out IVL performance tests, and IVL equipment is tested using Mc Science M6100.Device data pair
It is more as shown in the table than data test:
Such as Fig. 3, shown in Fig. 4, contrasted by device data, Devices Electroluminescent wavelength is mainly photic by Ir complexs itself
Luminous decision, under identical conditions, the PLQE trend of the efficiency of device also with Ir complexs in itself is consistent.Therefore, originally
The iridium of the disclosed high PLQE of invention poly-substituted quinoline coordination is miscellaneous can be obtained with compound in other devices it is redder than existing
The higher device efficiency of luminescent material.
The iridium of 13 poly-substituted quinoline of the present invention of embodiment coordination is miscellaneous to match somebody with somebody application of the compound in terms of OLED
The iridium of poly-substituted quinoline coordination described herein is miscellaneous to be applied to various optics and photoelectric device, example with Compound Compound
The light absorption device as solar energy and light sensor, optical transmitting set or existing light absorbs have again the device of photoemissivity with
And the mark for biologic applications.Poly-substituted quinoline of the present invention is matched somebody with somebody by taking Organic Light Emitting Diode (OLED) as an example below
The iridium of position is miscellaneous to be described with application of the compound in terms of photoelectric device.
Fig. 1 shows OLED 1000 sectional drawing, as illustrated, OLED 1000 is located at matrix comprising an anode 1004
On 1002, its material is transparent material, such as tin indium oxide；Hole transport material (HTL) 1006 and the phase of anode 1004
Even；Light emitting functional layer 1008 is located on hole transport material 1006, and the light emitting functional layer 1008 includes emitter and master
The luminescent material of body；The metal cathode layer 1012 of electron transport material (ETL) 1010 and one is set in turn in light emitting functional layer
On 1008.The OLED and similar luminescent device can include individual layer or lamination.In all senses, any layer of the list or lamination
Tin indium oxide (ITO), MoO can be included3、Ni2O3, poly- (3,4- ethene dioxythiophenes) (PEDOT), kayexalate
(PSS), 4,4', 4 "-((E of 1E, 1'E, 1 ")-cyclopropane -1,2,3- trimethylenes three (Cyano-methyl subunit)) three (2,3,5,
6- tetrafluoros cyanophenyl) (NHT-49), 2,2'- (perfluorodecalin -2,6- diyls) malononitrile (NHT-51), the cyanogen of 2,3,5,6- tetrafluoros four
Base-paraquinones bismethane (F4-TCNQ), N, N '-two -1- naphthyls-N, N '-biphenyl -1,1 '-biphenyl -4,4 ' diamines (NPD), 1,1-
Along ((two -4- p-totuidines bases) phenyl) hexamethylene (TAPC), 2,6- is along (N- carbazyls)-pyridine (mCpy), 2,8- along (folded
Nitrogen diphenyl phosphate) dibenzothiophenes (PO15), LiF, LiQ, Cs2CO3、CaCO3, Al or its composition.It is specific real at this
Apply in mode, the iridium that light emitting functional layer 1008 can include poly-substituted quinoline of the present invention coordination is miscellaneous with one or more in compound
Individual compound, this experimental selection use complex of iridium 7, optionally a related material of main part.ETL layers 1010 and 1006 also may be used
Iridium comprising the coordination of one or more poly-substituted quinolines it is miscellaneous with compound and with the hand-to-hand another implanted layer of electricity.The material of implanted layer
Material may include (electron injecting layer) EIL, (hole injection layer) HIL and CPL (cap rock), and its form can be simple layer or be dispersed in
In transmission material.Material of main part can be any suitable material of main part known in the art.OLED glow color is by sending out
The luminous energy (optical energy gap) of light functional layer 1008 determines, by being tuned processing and/or main body material to luminophor
The electronic structure of material tunes the luminous energy of light emitting functional layer 1008 (optical energy gap).Hole transport material in htl layer 1006
Electron transport material in material and ETL layers 1010 can include any suitable hole transporter known in the art.
The complex of iridium 7 of embodiment 14 is in CH2Cl2, spectrum test in PMMA
The complex of iridium 7 for testing prepared is placed in CH2Cl2, PMMA and carries out spectrum test, as a result as shown in Fig. 2
As can be seen that can launch under the exciting of different exciting lights very strong in emission spectrum obtained by the measurement of this experiment
Fluorescence, two main peaks are respectively in 629nm and 630nm, therefore complex of iridium 7 can be used for preparing the deep red light-emitting of high saturation
Device
The electroluminescent spectrum of the device of the complex of iridium 7 of embodiment 15.
Electroluminescent spectrum test is carried out as device prepared by luminescent material to complex of iridium 7, as a result as shown in Figure 5,
Illustrate that complex of iridium 7 belongs to high saturation feux rouges, this material can fully meet the chromaticity requirements of the feux rouges in display.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (9)
1. a kind of iridium of poly-substituted quinoline coordination is miscellaneous to match somebody with somebody compound, there is following molecular structural formula：
Ra,Rb,Rc ReRepresent hydrogen atom, D-atom, (related substituents can be by for (C1-C6) alkyl substituent or aryl substituent
It is deuterated, contain (C1-C6) alkyl substitution or aryl substitution), RdRepresent hydrogen atom or (C1-C6) alkyl substituent, Rf,RhGeneration
Table (C1-C6) alkyl substituent and aryl substituent (related substituents can by it is deuterated, substitute containing (C1-C6) alkyl or
Aryl substitutes).
2. a kind of iridium of poly-substituted quinoline coordination is miscellaneous according to claim 1 matches somebody with somebody compound, it is characterised in that, (the C1-
C6) the alkyl containing 1-6 carbon atom of alkyl groups mean linear or side chain, this kind of alkyl include methyl, ethyl, n-propyl, different
Propyl group, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, 1- methyl butyls, 2- methyl butyls, 3- methyl butyls, 1,2- dimethyl
Propyl group, 2,3- dimethyl propyls and 1- ethyl propyls, cyclopenta, cyclohexyl, 2- methyl -3- amyl groups, 3,3- dimethyl -2- fourths
Base.
3. the iridium of poly-substituted quinoline coordination is miscellaneous according to claim 1 matches somebody with somebody compound, it is characterised in that the poly-substituted quinoline
The miscellaneous molecular structural formula with compound of iridium of coordination can be divided into following six kinds of structures, be respectively designated as molecular formula II, molecular formula III,
Molecular formula IV, molecular formula V, molecular formula VI or molecular formula VII:
Molecular formula II:Ra-c、RfFor D-atom, (C1-C6) alkyl substituent or aryl substituent, Rd(C1-C6) alkyl is represented to take
Dai Ji；
Molecular formula III:Rb-c、RfD-atom is represented, (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-C6) alkyl
Substituent；
Molecular formula IV:Ra-b、RfD-atom is represented, (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-C6) alkyl
Substituent；
Molecular formula V:Rb-c,Re,RfD-atom is represented, (C1-C6) alkyl substituent or aryl substituent；
Molecular formula VI:Ra-b、Re,RfD-atom is represented, (C1-C6) alkyl substituent or aryl substituent, RdRepresent (C1-C6) alkane
Base substituent；
Molecular formula VII:Ra-c、Re-fD-atom is represented, (C1-C6) alkyl substituent or aryl substituent.
4. the iridium of poly-substituted quinoline coordination is miscellaneous according to claim 1 matches somebody with somebody compound, it is characterised in that：The poly-substituted quinoline
The miscellaneous iridium of coordination with compound is matched somebody with somebody from the miscellaneous iridium that is coordinated with compound 1 to poly-substituted quinoline of the iridium being coordinated by poly-substituted quinoline is miscellaneous
Selected in the group that compound 225 forms.
5. the iridium of poly-substituted quinoline coordination is miscellaneous according to claim 1 matches somebody with somebody compound, it is characterised in that:The poly-substituted quinoline
The miscellaneous iridium of coordination with compound is complex of iridium 6, and complex of iridium 7, complex of iridium 8, complex of iridium 11, complex of iridium 82, iridium is matched somebody with somebody
Compound 126, complex of iridium 157, complex of iridium 187, complex of iridium 201.
6. a kind of miscellaneous method with compound of iridium for synthesizing poly-substituted quinoline coordination described in claim 1, its synthesis path are as follows:
3,5 disubstituted (R in the ligand modified phenyl including 2 substitutionsd Rd), 4 substitution (Re) and 3,4,5 three substitution (Rd Re
Rd) phenyl, the iridium of poly-substituted quinoline coordination is miscellaneous to be with the specific synthesis path of compound：By under amine ester exchange reaction, acid catalysis
Skraup ring-closing condensation reactions and hydroxyhalide reaction generate polysubstituted quinoline, then can be obtained by Suzuki coupling reactions
The reaction and multiple reaction sites being coupled to part, the suzuki that (chemical equation as implied above) this path avoids alkyl are competing
The side reaction striven, combined coefficient can be improved and reduce purification difficulty；
Above-mentioned Ra,Rb,RcRepresent H (either deuterium) atoms or (C1-C6) alkyl substituent and aryl substituent (related substituents
Can by it is deuterated, substitute containing (C1-C6) alkyl or aryl substitutes)；RdRepresent H atom or (C1-C6) alkyl substituent, Re
Representative represent H (either deuterium) atoms or (C1-C6) alkyl substituent and aryl substituent (related substituents can by it is deuterated,
Contain the substitution of (C1-C6) alkyl or aryl substitution)；Rf,RhIt is (related to take to aryl substituent to represent (C1-C6) alkyl substituent
For base can by it is deuterated, substitute containing (C1-C6) alkyl or aryl substitutes).
7. one kind synthesizes complex of iridium 11 as claimed in claim 5, complex of iridium 82, complex of iridium 126, complex of iridium 157, iridium
Complex 187, complex of iridium 201, the method for complex of iridium 6, its synthesis path difference are as follows：The synthesis path of complex of iridium 11
For:
(1) 4'- methyl-[1,1'- biphenyl] -4- amine, 2- phenylacetyls ethyl acetate and dimethylbenzene mixing, N2 bubblings three are divided
Afterwards, stir under the conditions of 145 DEG C, TLC (petroleum ethers：Ethyl acetate=5:1) display reaction is complete, is cooled to room temperature, filters, after drying
Obtain faint yellow product N- (4'- methyl-[1,1'- xenyls] -4- bases) -3- oxo -2- phenylbutanamides；
(2) under nitrogen protection, the concentrated sulfuric acid is added dropwise to N- (4'- methyl-[1,1'- xenyl] -4- bases) -3- oxo -2- benzene dropwise
Base butyramide, 50 DEG C are heated to, stirred, TLC (petroleum ethers：Ethyl acetate=1:1) display reaction is complete, is cooled to room temperature, pours into
In frozen water, solid separates out, and filtration drying obtains faint yellow product 4- methyl -3- phenyl -6- (p-methylphenyl) quinoline -2- alcohol；
(3) under nitrogen protection, POCl3 is added dropwise in 4- methyl -3- phenyl -6- (p-methylphenyl) quinoline -2- alcohol, adds
Heat is stirred to TLC (petroleum ethers to 100 DEG C：Ethyl acetate=1:1) display reaction is complete, and reaction solution is cooled into room temperature, slowly falls
Enter frozen water, solid separates out, and filters, and washing, is dried to obtain chloro- 4- methyl -3- phenyl -6- (p-methylphenyl) quinolines of faint yellow product 2-
Quinoline；
(4) it is chloro- 4- methyl -3- phenyl -6- (p-methylphenyl) quinoline of 2-, 3,5- diformazan phenyl boric acids, three water potassium phosphates, 2- is bicyclic
Hexyl phosphine -2', 6'- dimethoxy-biphenyl, three (dibenzalacetone) two palladium and toluene mixing, nitrogen displacement reaction bulb atmosphere,
Reaction system is heated to 100 DEG C, stirred to TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, reaction solution second
Acetoacetic ester dilutes, and filtering, filtrate was spin-dried for post (petroleum ether：Ethyl acetate=50:1) white 2- (3,5- 3,5-dimethylphenyls)-
4- methyl -3- phenyl -6- (p- tolyl) quinoline；
(5) by 2- (3,5- 3,5-dimethylphenyl) -4- methyl -3- phenyl -6- (p- tolyl) quinoline, three water iridous chlorides, second two
Alcohol ether and water are mixed, nitrogen displacement reaction bulb atmosphere, and room temperature is cooled to after heating stirring, and solid separates out, and filters, is dried to obtain production
Thing dimer (30mg, 71%)；
(6) by dimer 11, pentane -2,4- diketone (0.1ml), sodium carbonate and ethylene glycol ethyl ether mixing, nitrogen displacement reaction bulb
Atmosphere, it is heated to reflux, is cooled to room temperature to solid and separates out, filtering, solid crosses post (petroleum ether：Ethyl acetate=30:1) red is obtained
Complex of iridium 11；
The synthesis path of complex of iridium 126 is：
(1) para-totuidine, 3- oxygen -3- p-methylphenyls-ethyl propionate and dimethylbenzene, reaction system N are added to tube sealing2Bubbling three divides
Afterwards, under the conditions of 145 DEG C stirring to TLC (petroleum ethers：Ethyl acetate=5:1) display reaction is complete, is cooled to room temperature, will separate out product
Filtering, dry white product 3- oxos-N, 3- bis--p- tolyl propionamide；
(2) under nitrogen displacement reaction bulb atmosphere, the concentrated sulfuric acid is added dropwise dropwise into 3- oxos-N, 3- bis--p- tolyl propionamide,
50 DEG C are heated to, is stirred to TLC (petroleum ethers：Ethyl acetate=3:1) display reaction is complete, is cooled to room temperature, pours into frozen water, Gu
Body separates out, and filtering, is dried to obtain white product 6- methyl -4- (p-methylphenyl) quinoline -2- alcohol；
(3) under nitrogen displacement reaction bulb atmosphere, POCl3 is added dropwise dropwise into 6- methyl -4- (p-methylphenyl) quinoline -2- alcohol,
Heating stirring is to TLC (petroleum ethers：Ethyl acetate=6:1) display reaction is complete, and reaction solution is cooled into room temperature, is poured slowly into frozen water
In, solid separates out, and filters, and washing, is dried to obtain chloro- 6- methyl -4- (p-methylphenyl) quinoline of white product 2-；
(4) by chloro- 6- methyl -4- (p-methylphenyl) quinoline of 2-, 3,5- diformazan phenyl boric acids, three water potassium phosphates, 2- dicyclohexyls phosphine -
2', 6'- dimethoxy-biphenyl, three (dibenzalacetone) two palladium and toluene mixing, nitrogen displacement reaction bulb atmosphere, are heated to
100 DEG C, stir to TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, and reaction solution is diluted with ethyl acetate, filtering,
Filtrate was spin-dried for post (petroleum ether：Ethyl acetate=50:1) it is (right to obtain white product 2- (3,5- 3,5-dimethylphenyls) -6- methyl -4-
Tolyl) quinoline；
(5) by 2- (3,5- 3,5-dimethylphenyl) -6- methyl -4- (p-methylphenyl) quinoline, three water iridous chlorides, ethylene glycol ethyl ether and
Water is mixed, nitrogen bubble three minutes, and room temperature is cooled to after heating stirring, and solid separates out, and filtering, is dried to obtain dimer 126；
(6) by dimer 126, pentane -2,4- diketone, sodium carbonate and ethylene glycol ethyl ether, nitrogen bubble three minutes, it is heated to reflux
Afterwards, reaction solution is cooled to room temperature, solid separates out, filtering, ether washing, is dried to obtain complex 126；
The method of complex of iridium 201, its synthesis path are：
(1) by 6- methyl -2,4- bis--p- tolyl quinoline, three water iridous chlorides, ethylene glycol ethyl ether and water mixing, nitrogen bubble
Three minutes, room temperature is cooled to after being heated to reflux, solid separates out, and filtering, is dried to obtain dimer 201；
(2) by dimer 201, pentane -2,4- diketone, sodium carbonate and ethylene glycol ethyl ether mixing, nitrogen bubble three minutes, heat back
After stream, reaction solution is cooled to room temperature, solid separates out, filtering, and ether washing, air drying obtains complex of iridium 201；
The synthesis path of complex of iridium 187 is：
(1) para-totuidine, 2,5- dimethyl -3- oxo-hexanoic acid ethyl esters and dimethylbenzene, reaction system N are added to tube sealing2Bubbling three
After point, stirred under the conditions of 145 DEG C to TLC (petroleum ethers：Ethyl acetate=5:1) display reaction is complete, and reaction solution is cooled into room
Temperature, product separate out, filtering, dry white 2,5- dimethyl -3- oxos-N- (p-methylphenyl) caproamide；
(2) 2,5- dimethyl -3- oxos-N- (p-methylphenyl) caproamide, nitrogen displacement reaction bulb atmosphere are added into three-neck flask
Enclose, the concentrated sulfuric acid is added dropwise to reaction system dropwise, 50 DEG C, stirs to TLC (petroleum ethers：Ethyl acetate=3:1) display reaction is complete,
Reaction solution is cooled to room temperature, poured into frozen water, solid separates out, and filtering, air drying obtains faint yellow 4- isobutyl groups -3,6- bis-
Methyl quinoline -2- alcohol；
(3) 4- isobutyl group -3,6- dimethyl quinoline -2- alcohol (800mg, 3.5mmol), nitrogen displacement reaction bulb atmosphere are added in a reservoir
Enclose, POCl3 is added dropwise to reaction system dropwise, 100 DEG C, stirs to TLC (petroleum ethers：Ethyl acetate=5:1) display has been reacted
Entirely, reaction solution is cooled to room temperature, poured into frozen water, solid separates out, and filters, and washing, is dried to obtain the chloro- 4- isobutyls of faint yellow 2-
Base -3,6- dimethyl quinolines；
(4) chloro- 4- isobutyl groups -3, the 6- dimethyl quinolines of 2-, 3,5- diformazan phenyl boric acids, three water phosphoric acid are added into chemical vessel
Potassium, 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyls, three (dibenzalacetone) two palladium and toluene, nitrogen displacement reaction bulb
Atmosphere, 100 DEG C are heated to, stirred to TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, reaction solution acetic acid second
Ester dilutes, and filtering, filtrate was spin-dried for post (petroleum ether：Ethyl acetate=10:1) it is different to obtain white 2- (3,5- 3,5-dimethylphenyls) -4-
Butyl -3,6- dimethyl quinolines (700mg, 55%)；
(5) by 2- (3,5- 3,5-dimethylphenyl) -4- isobutyl group -3,6- dimethyl quinolines, three water iridous chlorides, ethylene glycol ethyl ether and
Water mixes, nitrogen displacement reaction bulb atmosphere, after being heated to reflux, is cooled to room temperature, solid separates out, and filtering, air drying obtains dimerization
Body 187；
(6) by dimethylnonane -4, the 6- diketone of dimer 187,2,8-, sodium carbonate and ethylene glycol ethyl ether, nitrogen displacement reaction bulb
Atmosphere, after reaction system is heated to reflux, reaction solution is cooled to room temperature, solution was spin-dried for post (petroleum ether：Ethyl acetate=50:1)
Obtain the complex of iridium 187 of red；
The synthesis path of complex of iridium 82 is：
(1) by 4'- methyl-[1,1'- biphenyl] -4- amine, 5- methyl -3- oxos ethyl hexanoate and dimethylbenzene, reaction system N2Bubbling
After three points, stirred under the conditions of 145 DEG C to TLC (petroleum ethers：Ethyl acetate=5:1) display reaction is complete, and reaction solution is cooled into room
Temperature, product separate out, filtering, air drying obtain the faint yellow 5- methyl-N- of product (4'- methyl-[1,1'- xenyl] -4- bases) -
3- oxohexanoyl amine；
(2) nitrogen displacement reaction atmosphere, the concentrated sulfuric acid are added dropwise to 5- methyl-N- (4'- methyl-[1,1'- xenyl] -4- dropwise
Base) -3- oxohexanoyl amine, heating stirring to TLC (petroleum ethers：Ethyl acetate=3:1) display reaction is complete, is cooled to room temperature, falls
Enter in frozen water, solid separates out, and filters, and washing, air drying obtains white 4- isobutyl groups -6- (p-methylphenyl) quinoline -2- alcohol
(15.5g, 95%)；
(3) nitrogen displacement reaction atmosphere POCl3 is added dropwise to 4- isobutyl groups -6- (p-methylphenyl) quinoline -2- alcohol dropwise, heating
Stir to TLC (petroleum ethers：Ethyl acetate=6:1) display reaction is complete, and reaction solution is cooled into room temperature, poured into frozen water, solid
Separate out, filter, washing, dry chloro- 4- isobutyl groups -6- (p-methylphenyl) quinoline of buff 2-；
(4) chloro- 4- isobutyl groups -6- (p-methylphenyl) quinoline of 2- will be added in 500ml round-bottomed flasks, to methylphenylboronic acid, three water
Potassium phosphate, 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyls, three (dibenzalacetone) two palladium and toluene, nitrogen displacement are anti-
Atmosphere is answered, is heated to reflux to TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, and reaction solution is diluted with ethyl acetate,
Filtering, filtrate were spin-dried for post (petroleum ether：Ethyl acetate=10:1) white product 2- (4- aminomethyl phenyls) -4- isobutyl groups -6- is obtained
(p-methylphenyl) quinoline；
(5 by 2- (4- aminomethyl phenyls) -4- isobutyl groups -6- (p-methylphenyl) quinoline, three water iridous chlorides, ethylene glycol ethyl ether and water
Mixing, nitrogen displacement reaction bulb atmosphere, is heated to reflux, and is cooled to room temperature, and solid separates out, filtering, ether washing it is dry dimer
82；
(6) by dimethylnonane -4, the 6- diketone of dimer 82,2,8-, sodium carbonate and ethylene glycol ethyl ether, nitrogen displacement reaction bulb atmosphere
Enclose, after being heated to reflux, be cooled to room temperature, be spin-dried for post (petroleum ether：Dichloromethane=1:1) complex of iridium 82 of red is obtained；
The synthesis path of complex of iridium 157 is as follows：
(1) by 4- isobutyl groups -6- (p- tolyl) -2- (3,4,5- trimethylphenyl) quinoline, three water iridous chlorides, ethylene glycol
Ether and water, nitrogen displacement reaction bulb atmosphere, after being heated to reflux, cooling solid separates out, filtering, dry dimer 157；
(2) by dimethylnonane -4, the 6- diketone of dimer 157,2,8-, sodium carbonate and ethylene glycol ethyl ether, nitrogen displacement reaction bulb
Atmosphere, it is heated to reflux, cools down, be spin-dried for, crosses post (petroleum ether：Ethyl acetate=30:1) complex of iridium 157 of red is obtained,
The synthesis path of complex of iridium 6 is as follows：
(1) by 4'- methyl-[1,1'- biphenyl] -4- amine, 2,5- dimethyl -3- oxos ethyl hexanoates and dimethylbenzene mixing, reaction
System N2After bubbling three divides, stirred under the conditions of 145 DEG C to TLC (petroleum ethers：Ethyl acetate=5:1) display reaction is complete, is cooled to
Room temperature, product separate out, filtering, dry faint yellow product 2, and 5- dimethyl-N -s (4'- methyl-[1,1'- xenyl] -4- bases) -
3- oxohexanoyl amine；
(2) nitrogen displacement reaction bulb atmosphere, the concentrated sulfuric acid are added dropwise to 2,5- dimethyl-N -s (4'- methyl-[1,1'- biphenyl dropwise
Base] -4- bases) -3- oxohexanoyl amine, heating stirring to TLC (petroleum ethers：Ethyl acetate=3:1) display reaction is complete, will react
Liquid is cooled to room temperature, is poured slowly into frozen water, and solid separates out, and filtering, air drying obtains yellow product 4- isobutyl group -3- first
Base -6- (p-methylphenyl) quinoline -2- alcohol；
(3) nitrogen displacement reaction bulb atmosphere, POCl3 be added dropwise to dropwise 4- isobutyl group -3- methyl -6- (p-methylphenyl) quinoline -
2- alcohol, heating stirring to TLC (petroleum ethers：Ethyl acetate=6:1) display reaction is complete, and reaction solution is cooled into room temperature, pours into ice
In water, solid separates out, and filters, and washing, is dried to obtain chloro- 4- isobutyl groups -3- methyl -6- (p-methylphenyl) quinolines of yellow product 2-
Quinoline；
(4) it is chloro- 4- isobutyl groups -3- methyl -6- (p-methylphenyl) quinoline of 2-, 3,5- diformazan phenyl boric acids, three water potassium phosphates, 2- is double
Cyclohexyl phosphine -2', 6'- dimethoxy-biphenyl, three (dibenzalacetone) two palladium and toluene mixing, nitrogen displacement reaction bulb atmosphere
Enclose, heating stirring to TLC (petroleum ethers：Ethyl acetate=10:1) display reaction is complete, and reaction solution is diluted with ethyl acetate, mistake
Filter, filtrate were spin-dried for post (petroleum ether：Ethyl acetate=50:1) white product 2- (3,5- 3,5-dimethylphenyls) -4- isobutyl groups -
3- methyl -6- (p- tolyl) quinoline；
(5) by 2- (3,5- 3,5-dimethylphenyl) -4- isobutyl group -3- methyl -6- (p- tolyl) quinoline, three water iridous chlorides, second
Glycol ether and water mix, nitrogen displacement reaction bulb atmosphere, after heating stirring, reaction solution are cooled into room temperature, solid separates out, mistake
Filter, ether washing, dry dimer 6；
(6) by dimer 6, pentane -2,4- diketone, sodium carbonate and ethylene glycol ethyl ether mixing, nitrogen displacement reaction bulb atmosphere, heating
Backflow, is cooled to room temperature, is spin-dried for, and crosses post (petroleum ether：Ethyl acetate=30:1) complex of iridium 6 of red is obtained.
8. the iridium of poly-substituted quinoline coordination is miscellaneous to match somebody with somebody application of the compound in terms of electroluminescent material.
9. the iridium of poly-substituted quinoline coordination is miscellaneous to match somebody with somebody application of the compound as electroluminescent material in photoelectricity electrical equipment.
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